Process for production of a polyurethane foam from a heat curable froth

ABSTRACT

PROCESS FOR PREPARING CURED POLYURETHANE FOAM CONSISTING ESSENTIALLY OF (1) FORMING A HEAT CURABLE POLYURETHANE-FORMING FROTH WHICH IS SUBSTANTIALLY STRUCTURALLY AND CHEMICALLY STABLE, BUT WORKABLE AT AMBIENT CONDITIONS AND (2) HEATING SAID FROTH AT A TEMPERATURE OF AT LEAST 70*C. TO FORM A CURED POLYURETHANE FOAM.

United States Patent Office US. Cl. 260--2.5 BD 20 Claims ABSTRACT OE THE DISCLOSURE Process for preparing cured polyurethane foam consisting essentially of (1) forming a heat curable polyurethane-forming froth which is substantially structurally and chemically stable, but workable at ambient conditions and (2) heating said froth at a temperature of at least 70 C. to form a cured polyurethane foam.

This application is a continuation-in-part of application 'Ser. No. 795,674 filed J an. 31, 1969, now abandoned.

This invention relates to novel heat curable polyurethane-forming froths having extensive utility in the production of molded polyurethane foam articles, foam backings for carpeting and fabrics, coatings for wire, cable and other articles, small cavity encapsulations and the like.

It has been the practice in the past manufacture of polyurethane foams to use relatively fast-acting components so that the gas bubbles generated to form the cells of the foam would be swiftly entrapped. In order to do this, the curing or polymerization must proceed at high speed with almost an instantaneous steep increase in viscosity. Since bubble formation or expansion as well as curing were taking place simultaneously, it was very difficult to control the size of an article formed by such methods as knife coating before it set and became unworkable. Hence molding methods are wirely used commercially to control the size of articles produced from polyurethane foams.

Moreover, as noted in Hankins US. Pat. No. 3,046,177 and in Voelker US. Pat. No. 3,181,199, Unexpected irregularities in performance. make the long distance movement of polyurethane froth highly disadvantageous. Also, when the expandingsmixture is applied to rough surfaces such as the back of a carpet, it would expand to substantially the same'degree throughout and reproduce a rough or uneven surface on the resulting foam. Both of the above-mentioned patents teach the immediate formation and shaping of the foam.

The prior art is further exemplified by Hoppe, US. Pat. No. 3,188,296 wherein polyurethane forming reactants are so fast acting one must be injected into the other under extremely high pressures, such as 15,000 p.s.i. and airunder pressure must be tangentially injected in special equipment to produce a turbulent flow. The air then .acts as anucleating agent for the foaming gas produced by the chemical reaction. The rate of reaction is so fast that, as stated in the patent, the mixing normally takes place in 0.5 to 25 seconds.

Violent mixing of the reactive ingredients and catalyst is employed in the process disclosed in the Hankins US. Pat. No. 3,046,177. In this process, the polymerization begins almost instantaneously in the special mixer provided and the reacting mixture is almost instantaneously discharged onto a mold surface where it is simultaneously distributed and shaped with air jets as it is in its final stages of expansion.

Patented Nov. 13, 1973 In another case, as described in Knox, US. Pat. No. 3,108,976, the froth is first formed by decompression of the reactants and air under high pressure and then mixed with the other reactant and cured or it is first formed by decompression of both reactants and highly pressurized air and then mixed with the catalyst or cross-linker and cured.

According to the present invention, a novel froth is provided which is substantially structurally and chemically stable but workable at ambient conditions, i.e., capable of being transported for considerable distances and/or temporarily stored and then shaped and formed, and can still be rapidly cured to a tack-free condition when desired by the application of heat, as by raising the temperature of the froth to 70 C. or more. The novel froths contain, as the substantially non-aqueous liquid phase, stable polyurethane-forming components, i.e., components that are substantially reactive with each other only at a temperature of at least 70 C. or higher and a surfactant for structurally stabilizing the froth until it is cured by heating and, as the gas or bubble phase, an inert gas, such as air, uniformly dispersed throughout the liquid phase in the form of tiny bubbles or cells. Thus a heat curable froth is provided which is substantially structurally and chemically stable but workable at ambient conditions, comprising, a mixture reactive at temperatures above about 70 C. to form a polyurethane, said mixture containing a polyisocyanate, an active hydrogen compound reactive with said polyisocyanate to form a polyurethane, and a surfactant for structurally stabilizing said froth until cured by heating to a temperature of at least 70 C. to produce a cured froth; and an inert normally gaseous gas substantially uniformly dispersed throughout said mixture to form said froth.

The novel froth can contain a catalyst and/or a crosslinking agent so long as its presence will not initiate substantial polymerization at ambient temperatures. Other additives for providing special effects, e.g., coloring agents, fillers, etc. can also -be included so long as they do not initiate substantial polymerization at ambient temperatures.

The liquid phase is substantially chemically stable and does not undergo substantial polymerization when the viscosity of a teat admixture containing only the nonfrothed mixed polyurethane-forming components, surfactants, and any catalysts composing the liquid phase does not reach about 10,000 centipoises in 2600 seconds when held at a temperature in the range of 24.5 to 25.5 C. The materials are present in the test admixture in the same relative amounts as in the mixture used to produce the froth. The liquid phase can be thus characterized by mixing only those ingredients for about one minute and placing 7.5 ml. of it in a Brookfield LVT Viscometer equipped with a jacketed small sample chamber, holding it at a temperature of 24.5 to 255 C. and determining its viscosity over the above-specified period of time. The froth is rapidly heat curable when a one-quarter inch thick section of it cures to a tack-free condition within about 30 minutes at about C.

Thus the instant invention also provides a process for preparing a cured polyurethane foam consisting essentially of 1) forming a substantially non-aqueous mixture comprising (a) An organic polyisocyanate,

(b) An active hydrogen-containing compound substantially reactive with said polyisocyanate only at a temperature of at least 70 C. to form a polyurethane,

(c) An organosilicon surfactant for structurally stabilizing the froth produced according to step (2) below, during the period that the liquid phase of said froth is chemically stable and until said froth is cured by heating to a temperature of at least 70 C. to produce a cured foam, and

(d) A catalyst having substantial catalytic activity in the curing of said mixture only at temperatures of at least 70 C., and (2) substantially uniformally dispersing inert gas throughout the mixture by mechanical heating of said mixture to form a heat curable froth which is substantially structurally and chemically stable, but workable at ambient conditions, wherein (i) Said froth is free of auxiliary blowing agents,

(ii) Components (a), (b), (c) and ((1) above, present in the liquid phase of said froth are such that an unfrothed admixture containing only (a), (b), (c) and (d) in the same proportions (a), (b), (c) and (d) are present in the liquid phase of said froth is chemically stable to the extent that the admixture retains a viscosity of not greater than 10,000 cps. for about 2600 seconds at 25 C.i0.5 C.;

(iii) Said froth has a density of not greater than 45% of the density of the unfrothed liquid phase; and

(iv) A /1 inch section of said froth is curable to a tack free condition in not more than about 30 minutes at a temperature of 125 C.; and

(3) Heating said froth at a temperature at least 70 C. to form a cured polyurethane foam, any further expansion of said froth during heat curing being substantially only thermal expansion of said inert gas employed.

The polyisocyanate components employed in this invention for mixing with active hydrogen compounds to form the liquid phase of our novel froths preferably are those having the general formula:

wherein i is an integer of two or more and Q is an organic radical having the valence of i. Q can be substituted or unsubstituted hydrocarbon group (e.g., an alkylene or an arylene group). Q can be a group having the formula QZQ' where Q' is an alkylene or arylene group and Z is O, OQ, CO-, S,

or SO Examples of such compounds include hexamethylene diisocyanate, 1,8-diisocyanato-p-methane, xylyl diisocyanate, (OCNCH CH CH OCH O) l-methyl- 2,4-diisocyanatocyclohexane, phenylene diisocyanates, tolylene diisocyanates, chlorophenylene diisocyanates, diphenylmethane-4,4'-diisocyanate, naphthalene-l,5-diisocyanate, triphenylmethane-4,4',4"triisocyanate, and isopropylbenzene-alpha-4-diisocyanate.

Q can also represent a polyurethane radical having a valence of i in which case Q(NCO) is a composition conventionally known as a prepolymer. Such prepolymers are formed by reacting a stoichiometric excess of a polyisocyanate as set forth hereinbefore and hereinafter with an active hydrogen-containing component as set forth hereinafter, especially the polyhydroxyl-containing materials or polyols described below. Usually, for example, the polyisocyanate is employed in proportions of from about 30 percent to about 200 percent stoichiometric excess, the stoichiometry being based upon equivalents of isocyanate group per equivalent of hydroxyl in the polyol.

Further included among the isocyanates useful in this invention are dimers and trimers of isocyanates and diisocyanates and polymeric diisocyanates such as those having the general formula:

in which i and j are each integers of two or more, and Q" is a polyfunctional organic radical, and/or, as additional components in the mixtures, compounds of the general formula:

in which i is one or more and L is a monofunctional or polyfunctional atom or radical. Examples of this type include ethylphosphonic diisocyanate, C H P(O) (NCO) phenylphosphonic diisocyanate, C H P(O) (NCO) com- 4 pounds containing a ESl--NCO group, isocyanates derived from sulfonamides (QSO NCO), c'yanic acid, and thiocyanic acid.

More specifically, the polyisocyanate component employed in the polyurethane-forming froths of this invention also include the following specific compounds as well as mixtures of two or more of them; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, crude tolylene diisocyanate, bis(4-isocyanatophenyl)methane, polyphenylmethylene polyisocyanates that are produced by phosgenation of anilineformaldehyde condensation products:

dianisidine diisocyanate,

toluidine diisocyanate,

xylylene diisocyanate, bis(Z-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, bis(2-isocyanatoethyl) carbonate, l,6-hexamethylenediisocyanate, 1,4-tetramethylene-diisocyanate,

l, lO-decamethylenediisocyanate, cumene-2,4-diisocyanate, 4-ethoxy-l,3-phenylenediisocyanate, 4-chloro-1,3-phenylenediisocyanate, 4-bromo-1,B-phenylenediisocyanate, 4-ethoxy-1,3-phenylenediisocyanate, 2,4'-diisoeyanatodiphenylether, 5,6-dimethyl-1,3phenylenediisoc'yanate, 2,4-dimethyl-1,3phenylenediisocyanate, 4,4'-diisocyanatodiphenylether,

bis 5,6-(2-isocyanatoethyl) bicyclo[2.2.1]hept-2-ene, benzidinediisocyanate, 4,6-dimethyl-l,3-phenylenediisocyanate, 9,10-anthracenediisocyanate, 4,4'-diisocyanatodibenzyl, 3,3-dimeth'yl-4,4'-diisocyanatodiphenylmethane, 2,6-dimethyl-4,4'-diisocyanatodiphenyl, 2,4-diisocyanatostilbene, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 3,3'-dimethoxy-4,4'diisocyanatodiphenyl, '1,4-anthracenediisocyanate, 2,5-fluorenediisocyanate, 1,8naphthalenediisocyanate, 2,6diisocyanatobenzfui'an, 2,4,6-toluenetriisocyanate, and

many other organic polyisocyanates that are known in the art, such as those that are disclosed in an article by Siefken, Ann., 562, 75 (1949). In general, the aromatic polyisocyanates are preferred because of their greater reactivity.

It is also of considerable advantage to block the isocyanate groups of the polyisocyanates listed above with a monofunctional organic compound such as a phenol as described in Annalen, vol. 262, pp. 205 to 229; Reinhold Plastics Applications Series on Polyurethanes by Bernard A. Dombrow, published by Reinhold Publishing Corporation, New York; 1957; and Polyurethanes: Chemistry And Technology I. Chemistry by Saunders & Frisch, pp. 118 to 121, published by Interscience in 1963. Blocking techniques permit the use of the more highly reactive polyisocyanates and/or to adjust the polymerizing or curing temperature of the froth. One or any number of the isocyanate groups in the polyisocyanate molecule can be blocked to provide the degree of reactivity desired. In addition, catalyst such as those described in Bunge US. Pat. No. 2,886,555 can be employed to adjust the splitting or unblocking temperature to that desired.

The amount of polyisocyanate employed will vary slightly depending upon the nature of the polyurethane being prepared. In general, the total NCO equivalent to total active hydrogen equivalent should be such as to provide a ratio of 0.8 to 2.0 equivalents of NCO per equivalent of active hydrogen, e.g., hydroxyl hydrogen, of the active hydrogen reactant, and preferably a ratio 5. of about 1.0 to 1.5 equivalents of -NCO per active hydrogen. H I

The active hydrogen-containing component includes polyhydroxyl-containing compounds, I such as, v the vhydroxyl-terminated polyhydrocarbons (US. Pat. No. 2,877,- 212); hydroxyl-terminated polyformals (US. Pat. No. 2,870,097); fatty acid triglycerides (U.S. Pat. Nos. 2,833,- 730 and 2,878,601); hydroxyl-terminated polyesters (US. Pat. Nos. 2,698,838, 2,921,915, 2,591,884, 2,866,762, 2,850,476, 2,602,783, 2,729,618, 2,779,689, 2,811,493, and 2,621,166); hydroxymethyl-terminated perfluoromethylenes ('U.S. Pat. Nos. 2,911,390 and 2,902,473); polyalkyleneether glycols (US. Pat. No. 2,808,391; British Pat. No. 733,624); polyalkylenearyleneether glycols (US. Pat. No. 2,808,391); polyalkyleneether triols (US. Pat. No. 2,866,774).

Especially preferred .polyhydroxyl-containing materials are the polyether polyols obtained by the chemical addition of alkylene oxides, such as, ethylene oxide, propylene oxide and mixtures thereof, to water or polyhydric organic compounds, such as ethylene glycol, propylene glycol, tri methylene glycol, 1,2-butylene glycol, 1,3-butanediol, 1,4- butanediol, 1,5 pentanediol, 1,2-hexylene glycol, 1,10- decanediol, 1,2 cyclohexanediol, 2 butene-1,4-diol, 3- cyclohexene- 1, l-dirnethanol, 4-methyl-3-cyclohexene-1,1- dimethanol, 3-methylene-1,S-pentanediol, diethylene glycol, (2-hydroxyethoxy)-1-propanol,4-(2-hydroxyethoxy)- l-butanol, 5-(2-hydroxypropoxy)-l-pentanol, 1-(2-hydroxymethoxy) 2-hexanol, 1-(2-hydroxypropoxy)-2-octano1, 3 allyloxy 1,5-pentanediol, 2-allyloxymethyl-2-methyl-1,3- propanediol, [4,4 pentyloxy)-methyl]-1,3-propanediol, 3-(o-propenylphenoxy)-1,2-propanediol, 2,2-diisopropylidenebis(p-phenyleneoxy)diethanol, glycerol, 1,2,6-hex anetriol, 1, 1, l-trirnethylolethane, 1,1, l-trimethylolpropanm 3 (2-hydroxyethoxy)-1,2-propanediol 3-(2-hydroxypropoxy)-1,2-propanedio1 2,4-dimethyl-2-(2-hydroxyethoxy)- methylpentanediol-1,5; 1,1,1-tris[ (2-hydroxyethoxy) methyl] ethane, 1,1,1-tris[(2-hydroxypropoxy)-methyl]propane, diethylene glycol, dipropylene glycol, pentaerythritol, sorbitol, sucrose, lactose, alpha-methylglucoside, alpha-hydroxyalkylglucoside, novolac resins, phosphoric acid, benzenephosphori'c acid, polyphosphoric acids such as tripolyphosphoric acid and tetrapolyphosphoric acid, ternary condensation products, caprolactone and the like. The alkylene oxides employed in producing polyoxyalkylene polyols normally have from 2 to 4 carobn atoms. Propylene oxide and mixtures of propylene oxide with ethylene oxide are preferred. The polyols listed above can be used per so as the active hydrogen compound.

A preferred class of polyether polyols employed in this invention can be represented generally by the following formula H n ZQZ Ia wherein R is hydrogen or a polyvalent hydrocarbon radical; a is an integer (e.g., 1 or 2 to 6 to 8) equal to the valence of R, n in each occurrence is an integer from 2 to 4 inclusive (preferably 3) and z in each occurrence is an integer having a value of from 2 to about 200, preferably from 15 to about 100. 1

Additional active hydrogen-containing materials are the polymers of cyclic esters having a reduced viscosity value of at least about 0.15, and desirably from about 0.2 to about 15, and higher. The preferred polymers of cyclic estershavea reduced viscosity value of from about 0.3 to about 10. These polymers are homopolymers or copolymers characterized as containing units of the formula:

wherein each R, individually, is hydrogen, alkyl, halo, or alkoxy; wherein A is the oxy group wherein x is an integer from 1 to 4; wherein y is an integer from 1 to 4; wherein z is an integer of zero or one; the sum of x+y+z arrazzt is at least 4 and not greater than 6; and the totalnurnber of R groups which are substituents other than hydrogen does not exceed 3, preferably does not exceed 2. Illustra-. tive R groupsincludemethyl, ethyl, isopropyl, n-butyl, sec-butyl, t-butyl, hexyl, chloro,-bromo,iodod, methoxy, ethoxy, n-butoxy, n-hexoxy, 2-ethylhex0xy, dodecoxy, and the like. It ispreferred that each. R, individually, be hydrogen, lower alkyl, eg, methyl,,ethyl, n-propyl, isobutyl, and/or lower alkoxy, e.g., methoxy, ethoxy, propoxy, n butoxy, and the like. It is further preferred that the total number of carbon atoms in the R substituents does not exceed eight.

In one embodiment, preferred polymers of cyclic esters contain both recurring structural Unit I and units of the formula:

L 1'! 1'1 V (II) wherein each R, individually, is hydrogen, alkyl, cycloalkyl, aryl, or chloroalkyl, or in which the two R variables together with the ethylene moiety of the oxyethylene chain of Unit II form a saturated cycloaliphatic hydrocarbon ring having from 4 to 8 carbon atoms, desirably from 5 to 6 carbon atoms and w is an integer of 1 or more, preferably 1 to 10. It is preferred that recurring Unit II contain from 2 to 12 carbon atoms. Illustrative R variables include methyl, ethyl, n-propyl, isopropyl, tbutyl, the hexyls, the dodecyls, 2-chloroethyl, phenyl, phenethyl, ethylphenyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like. It is preferred that R be hydrogen; lower alkyl, e.g., methyl, ethyl, n-propyl, isopropyl, chloroalkyl, e.g., 2-chloroethyl; and the like.

The aforedescribed recurring Unit (I) is interconnected through the oxy group (-O-) of one unit with the carbonyl group of a second unit, i.e., the interconnection does not involve the direct bonding of two carbonyl groups,

0n the other hand, the relatively low molecular weight cyclic ester polymers, e.g., those having reduced viscosity values below about 0.3 are characterized by end groups which can be hydroxyl or carboxyl. Cyclic ester polymers having an average molecular weight of about 500 to about 2000 are preferred for use herein.

The preparation of the cyclic ester polymers is well documented in the patent literature as exemplified by US. Pat. Nos. 3,021,309 through 3,021,317; 3,169,945; and 2,962,524. Briefly, the process involves the polymerization of a mixture containing at least one cyclic ester monomer with or without a functional initiator therefor such as the polyols described hereinbefore and in the patents mentioned above, and a suitable catalysts, the choice of which will depend on the presence or absence of added initiator. Suitable cyclic ester monomers which can be employed in the manufacture of the cyclic ester polymers are best illustrated by the following formula:

wherein the R, A, x, y, and 2 variables have the signifi-' operative conditions and, as noted in US. Pat. Nos. 3,021,309 to 3,021,317, in the presence of anionic catalysts. When reacting a mixture containing cyclic ester monomer and functional initiator which possesses at least one active hydrogen substituent, e.g., carboxyl or hydroxyl, it is desirable to use the catalysts noted in US. Pat. Nos. 2,878,236, 2,890,208, 3,169,945 and 3,284,417 under the operative conditions discussed therein. Suitable polyol initiators and polycarboxylic acid initiators are those listed in US. Pat. 3,169,945 and others of the patents enumerated herein as well as those polyols and polycarboxylic compounds listed hereinbefore.

Polymers of cyclic esters can also be manufactured via the process described in US. Pat. No. 2,962,524.

Cyclic ester/alkylene oxide copolymers can also be prepared by reacting a mixture comprising cyclic ester and alkylene oxide monomers, an interfacial agent such as a solid, relatively high molecular weight poly(vinyl stearate) or lauryl methacrylate/vinyl chloride copolymer (reduced viscosity in cyclohexanone at 30 C. of from about 0.3 to about 1.0), in the presence of an inert normally-liquid saturated aliphatic hydrocarbon vehicle such as heptane and phosphorus pentafiuoride as the catalyst therefor, at an elevated temperature, e.g., about 80 C., and for a period of time suflicient to produce such cyclic ester/alkylene oxide copolymers.

When the cyclic ester polymers are prepared from a mixture containing the cyclic ester monomer and minor amounts of a cyclic comonomer which is copolymerizable therewith, e.g., cyclic carbonates and cyclic ethers such as alkylene oxide, oxetane, tetrahydrofuran, etc., the polymeric chain of the resulting copolymeric product will be characterized by both recurring linear Unit I supra as well as the recurring linear Unit II (which would represent the alkylene oxide comonomer polymerized therein) and/ or by a recurring linear unit which would correspond to the additional polymerizable cyclic comonomer in the monomeric mixture. When the comonomer is an alkylene oxide, the resulting copolymeric product will contain both recurring linear Unit I and recurring linear Unit II in the copolymeric chain thereof. The interconnection of linear Unit I and linear Unit II supra does not involve or result in the direct bonding of two oxy groups, i.e., OO. In other words, the oxy group (O) of recurring linear Unit II is interconnected with the carbonyl group of recurring linear Unit I supra or with the alkylene moiety of a second oxyalkylene Unit (II).

Polymers of cyclic esters as described above are useful in producing polyurethane articles having comparatively high strength and elongation.

As mentioned previously, the polymers of cyclic esters which are contemplated are expressed in terms of their reduced viscosity values. As is well known in the art, reduced viscosity value is a measure or indication of the molecular weight of polymers. The expression reduced viscosity is a value obtained by dividing the specific viscosity by the concentration of polymer in the solution, the concentration being measured in grams of polymer per 100 milliliters of solvent. The specific viscosity is obtained by dividing the difference between the viscosity of the solution and the viscosity of the solvent by the viscosity of the solvent. Unless otherwise noted, the reduced viscosity values herein referred to are measured at a concentration of 0.2 grams of polymer in 100 milliliters of solvent (e.g., cyclohexanone, benzene, chloroform, toluene, or other common organic solvents) at 30 C.

Another type of active hydrogen-containing materials useful in this invention are the polymer/polyol compositions obtained by polymerizing ethylenically unsaturated monomers in a polyol as described in British Pat. No. 1,063,222 and US. Pat. No. 3,383,351, the disclosures of which are incorporated herein by reference. Suitable monomers for producing such compositions include acrylonitrile, vinyl chloride, styrene, butadiene, vinylidene chloride and other ethylenically unsaturated monomers as identified and described in the above-mentioned British patent and US. patent. Suitable polyols include those'listed and described hereinabove and in the British patent and US. patent. The polymer/polyol compositions can contain from about 1 to about 70 weight percent, preferably about 5 to about 50 weight percent, and most preferably about 10 to about 40 weight percent monomer polymerized in the polyol. Such compositions are conveniently prepared by polymerizing the monomers in the selected polyol at a temperature of 40 C. to 150 C. in the presence of a free radical polymerization catalyst such as peroxides, persulfates, percarbonate, perborates and azo compounds. Further details of the compositions and methods of making same are described in the above-mentioned British patent and US. patent. The resulting composition is believed to be a complex mixture comprising free polyol, free polymer and graft polymer/polyol complexes. Preparation l of the British patent is especially preferred. Polymer/polyol compositions of this type are useful in producing polyurethane articles having comparatively high load-bearing properties.

Mixtures of the above-active hydrogen-containing compounds can be employed as reactants with the polyisocyanate to form polyurethanes. For example, a mixture of a diol such as propylene glycol, polymer/polyol composition and cyclic ester polymer can be employed. Other illustrative mixtures include mixtures of polyether polyols; mixtures of polymer/polyol, dipropylene glycol and cyclic ester polymer; mixtures of polyether polyol, dipropylene glycol and polymer/polyol; mixtures of polyether polyol and dipropylene glycol and the like.

The polyol or polyol mixture employed in this invention can have hydroxyl numbers which vary over a wide range. In general, the hydroxyl numbers of the polyols or mixtures thereof, including other cross-linking additives, if employed, can range from about 28 to about 1000, and higher, preferably from about to about 800.

The hydroxyl number is defined as the number of milligrams of potassium hydroxide required for the complete neutralization of the hydrolysis product of the fully acetylated derivative prepared from 1 gram of polyol or mixtures of polyols with or without other cross-linking additives used in the invention. The hydroxyl number can also be defined by the equation:

wherein OH=hydroxyl number of the polyol.

f=average functionality, that is average number of hydroxyl groups per molecule of polyol.

M.W.=average molecular weight of the polyol.

The exact polyol or polyols employed depends upon the end-use of the polyurethane foam. The molecular weight and the hydroxyl number are selected properly to result in flexible, semi-flexible, or rigid foams. The polyol or polyols including cross-linking additives, if used, preferably possesses a hydroxyl number of from about 200 to about 1000 when employed in rigid foam formulations, from about 50 to about 250 for semi-flexible foams, and from about 45 to about 70 or more when employed in flexible foam formulations. Such limits are not intended to be restrictive, but are merely illustrtaive of the large number of possible combinations of the polyols that can be employed.

A wide variety of organosilicon surfactants can be employed herein for purposes of stabilizing the froth. A preferred stabilizer is an organosilicon copolymer consisting essentially of SiO (silicate) units and (CH SiO (trimethylsiloxy) units in a mol ratio of silicate to trimethylsiloxy units of about 0.811 to about 2.2:1, preferably about 1:1 to about 2.0:1, These copolymers, hereinafter called trimethylsiloxy-silicate copolymers, and procedures for making them are described in copending application, Ser. No. 664,641, filed Aug. 31, 1967, now abandoned.

A striking advantage in using the trimethylsiloxysilicate copolymers described above is their ability to synergistical- 1y, {retard .the-acatalytic .activity; at ambient temperatures of certain commonly used catalysts, such as dibutyltin dilaurate, while still permitting them to promote curing at elevated temperatures. This is especially important since it permits the use in this invention of catalysts which ordinarily would be too active to permit frothing without substantial curing at ambient temperatures.

Another preferred organosilicon surfactant stabilizer is the partially cross-linked siloxane-polyoxyalkylene block copolymer and mixtures thereof wherein the siloxane blocks and polyoxyalkylene blocks are linked by silicon to carbon, or by silicon to oxygen to carbon, linkages. The siloxane blocks are comprised of hydrocarbon-siloxane groups and have an average of at least two valences of silicon per block combined in said linkages. At least a portion of the polyoxyalkylene blocks are comprised of oxyalkylene groupsand are polyvalent, i.e., have at least two valences of carbon and/or carbon-bonded oxygen per block combined in said linkages. Any remaining poly oxyalkylene blocks are comprised of oxyalkylene groups and are monovalent, i.e., have only one valence of carbon or carbon-bonded oxygen per block combined in said linkages. x 7

Additionally, conventional organo polysiloxane-polyoxyalkylene block copolymers such as those described in Us. Pat. Nos. 2,834,748, 2,846,458, 2,868,824, 2,917,480 and 3,057,901 can be employed but are of lesser preference than the above-mentioned trimethylsiloxy-silicate copolymers and the partially cross-linked copolymers. Partially crosslinked copolymers and the trimethylsiloxysilicate copolymers are more useful with the non-prepolymer polyisocyanates; such as the monomeric polyisocyanates, for example, toluene diisocyanate.

The amount of the organosilicon polymer employed as a foam stabilizer in this invention can vary over Wide limits, e.g., from about 0.5 weight parts to 10 weight parts or greater, per hundred weight parts of the active hydrogen component. The is no commensurate advantage to using amounts of organosilicon copolymer foam stabilizer less than 0.5 or greater than about 10 weight parts on the same basis. Preferably, the amount of organosilicon copolymer present in the foam formulations varies from about 1.0 weight parts to about 6.0 Weight parts on the same basis.

Preferred catalysts include nickel acetylacetonate, more formally known as bis(2,4-pentanedionate)nickel (II), (diacetylacetonate nickel) and derivatives thereof such as diacetonitrilediacetylacetonato nickel, diphenylnitrilediacetylacetonato nickel, bis (triphenylphosphine)-diacetylacetonato nickel and the like. In addition, tin catalysts such as dibutyltin dilaurate can beused advantageously in the presence of the trimethylsiloxy-silicate copolymer surfactants described above. The amount of such catalyst employed in the liquid phase is preferably in the range of 0.03 to 3.0 weight parts per hundred weight parts of the active hydrogen compound.

' Some conventional metal catalysts in conventional concentrations can be used when the trimethylsiloxy-silicate copolymers are used as stabilizers. When other stabilizers areused, the conventional metal catalysts are used in low concentrations. Such catalysts include both inorganic metal compounds and metal compounds which contain organic groups. Particularly useful catalysts are organotin compounds. Thesecatalysts can be used each alone or in mixtures with one ormore of the. others. Among the organo-tin compounds are stannous acylates such as dialkyl tin salts of carboxylic acids, e.g., dibutyltin dilaurate.

Other but less .preferred latent catalysts which can be employed are the metal diorganodithiocarbamates where- 10 in the organo groups can be, for instance, alkyl groups of up to 18 carbon atoms and preferably from 1 to 8 carbon atoms. I

In certain systems, especially those having a highhydroxyl number, no catalyst at all is needed. As shown by the examples set forth hereinafter, certain systems containing no catalysts at all are substantially structurally and chemically stable at ambient temperatures yet are curble by the application of heat at temperatures above about 70 C. The hydroxyl number of one such system preferably exceeds 400. Other non-catalyst systems include those where one of the reactants is catalytic, e.g., where the active hydrogen-containing compound is a. strong base.

The liquid phase can contain other ingredients such as dyes, fillers, pigments, and other materials for providing desired effects. Small amounts of an auxiliary blowing agent can be employed. For example, high boiling fluorocarbons, e.g., boiling above about 40 C. can be used. Very small amounts of water, i.e., insufiicient to bring about any substantial gas evolution, can be employed. Specific fluorocarbons include the Ucon fluorocarbons and Freons boiling above about 40 C., for example 1,1,2- trichloro-1,2,2-trifluoroethane and isomers of tetrachlorodifluoroethane, tetrachloromonofluoroethane, and the like. The auxiliary agent, although it is not necessary, can be employed for purposes of providing an added expansion during heat curing in those cases where such added expansion is desired.

The gas phase of the novel froths is most preferably air because of its cheapness and ready availability. However, if desired, other gases can be used which are gaseous at ambient conditions and which are substantially inert or non-reactive with any component of the liquid phase. Such other gases include, for example, nitrogen, carbon dioxide and even fluorocarbons which are normally gaseous at ambient temperatures.

The inert gas is incorporated into the liquid phase by mechanical beating of the liquid phase in high shear equipment such as in a Hobart mixer or an Oakes mixer. The gas can be introduced under pressure as in the usual operation of an O-akes mixer or it can be drawn in from the overlying atmosphere by the beating or whipping action as in a Hobart mixer. The mechanical beating operation preferably is conducted at pressures not greater than to 200 p.s.i.g. It is significant, however, to note that conventional, readily available, mixing equipment is used and no special equipment is necessary.

The amount of inert gas beaten into the liquid phase should be adequate to provide a froth having a density at ambient atmospheric pressure of less than about 45%, preferably less than about 35%, of the density of the liquid phase prior to frothing. The mechanical beating is conducted over a period of a few seconds in an Oakes mixer, or of 3 to 30 minutes in a Hobart mixer, or however long it takes to obtain the desired froth density in the mixing equipment employed.

The froth as it emerges from the mechanical beating operation is substantially chemically stable and is structurally stable but easily workable at ambient temperatures, e.g., about 15 C. to about 30 C. The consistency of the froth closely resembles the consistency of aerosoldispensed shaving cream and it has a density of less than about 45%, or preferably less than about 35%, of the density of the liquid phase prior to frothing.

The novel froths of this invention find extensive utility in the production of shaped, foamed articles ranging from flexible foamed articles to rigid foamed articles and all degrees of flexibility and rigidity inbetween. For example, the noval froths can be molded and subsequently heat cured to form crash padded panels, dashboards, sunvisors, arm-rests and the like for automotive vehicles, airplanes and boats, and can be applied to and cured on the backs of carpeting to provide foam cushion backings 1 l or to textile fabrics to provide interlinings for padding and/or thermal insulation purposes.

Because of their substantial chemical and structural stability, the novel froths can be readily shaped by molds or doctor blades. Inasmuch as their is no substantial chemical expansion (i.e., expansion due to gas produced in the liquid phase by a chemical reaction) or expansion due to volatilization of a liquid and substantially only thermal expansion taking place during heat curing, dimensional changes are readily predictable and easily controlled. For these reasons, it is also possible to avoid duplication of rough surfaces such as in coating the rough and uneven backsides of carpets. This was not possible through the use of chemically expanded foams.

As will be seen in the following examples, the present invention now permits the selection of appropriate amounts and types of surfactants which provide an appropriate amount of drainage of the liquid phase, for example, into the interstices of a carpet back. This drainage upon subsequent heat curing not only locks the foam backing to the carpet but also serves the dual purpose of locking the fibers of the carpet back together. More specifically, this invention also provides a process for providing a second backing on a carpet material composed of a first backing having a front side faced with fibers which pass through the first backing and which extend beyond the back side to the first backing to mechanically anchor the fibers to the first backing, which process comprises applying to (a) the back side of the first backing and (b) the portion of the fibers extending beyond said back side a substantially uniformly thick layer of a froth of this invention, and curing the froth at a temperature above 70 C. to (a) form a cured polyurethane foam of substantially uniform thickness as an integral second backing on the back side of the first backing and (b) bond the fibers to the first backing. The first backing can be any conventional carpet backing material (e.g., jute or polypropylene) and the fibers can be mechanically anchored to the first backing by any conveneional means (e.g., by sewing or needle punching). The fibers can be composed of any conventional carpeting material (e.g., cotton, rayon, wool, nylon, acrylonitrile polymers, vinyl halide polymers, etc.). The fibers can be in any suitable form (e.g., in the form of pile yarns threaded through the first backing having cut or looped pile faces on the front side of the first backing). The froth can be applied to the first backing by any suitable procedure (e.g., knife coating). The backing can have any desired thickness (e.g., from A to /2 inch).

The novel froth is readily transportable by conveyor, suitable vehicle or piping from the site of its manufacture to the site of its use in coating the backs of carpeting or fabric, or in forming shaped articles by molding, or in coating wire or other articles, or in encapsulation operations.

The following illustrative examples are presented. All parts and percentages are on a weight basis, Me stands for the methyl group, Bu stands for the butyl group, all temperatures are on the centigrade scale, and all densities are in pounds per cubic foot unless otherwise specified.

EXAMPLE 1 Three mixtures were prepared containing the amounts in weight parts of the ingredients listed in Table I below. All mixtures possessed a viscosity of less than 10,000 cps. after holding at 24.5 to 25.5 C. for 2600 seconds and none of the mixtures gelled when held at ambient (room) temperature for more than one hour at which time the test was discontinued.

The mixtures were mechanically beaten in a S-quart Hobart N-50 mixer using a wire whip for ten minutes. Each mixture produced a low density froth which cured to a tack-free, flexible foam having a density below 45% of the density of the mixture before frothing.

In a comparative test, the trimethylsiloxy-silicate co- 12 polymer of mixture C was replaced with an equal weight amount of a surfactant copolymer having the average formula:

The resulting comparative mixture gelled in six minutes when held at ambient (room) temperature.

TABLE I t. B C

Polyol l 100 100 100 Dibutyltin dilaurate 0.1 0.2 0.4 l(CH3)3Si09.5]o.5[$i02]1.0 0. 0 6. O 6. 0 TDI 26.0 26.0 26.0

1 PolyolI as used herein designates 9. glycerol started propylene oxide adduet triol having an average molecular weight of about 1,000 and a hydroxyl number of 168 and having the average formula:

2 50 wt. percent in xylene. TDI as used herein designates a mixture of weight percent of 2,4. tolylene dnsocyanate and 20 weight percent of 2,6-toylyene diisocyanate- EXAMPLE 2 Composition A of Example 1 was repeated except that the dibutyltin dilaurate was replaced with 0.02 weight parts of stannous octoate. The resulting mixture had a viscosity of about 900 after holding it at 24.5 to 25.5 C; for 2600 seconds. A stable froth having a density of less than 45% of the liquid mixture was made from the mixture in the same manner as set forth in Example 1. When the froth was heated to 125 C. it cured to tack-free flexible foam in less than 10 minutes.

EXAMPLE 3 Nine mixtures were prepared from the following ingredients:

Wt. pts. Polyol II 1 TDI 105.8 Surfactant (listed in Table II) 10.0

1 Polyol II as used herein designates a glycerol started propylene oxide adduet triol having an average molecular weight of about 259 and a hydroxyl number of about 650 and having the average formula:

Saybolt Universal seconds at 100 F. in a 50:50 weight mixture.

. The siloxa'ne block has the average formula: MeaSiO[MezSi]1a[SiMoO] .5SiMe@; there are 1.1 moles per siloxane block of divalent polyox eth leno blocks of the average formula: C;H O(C H.O)1CzH bonded to silicon and 4.4 mols per siloxane block of monovalent polyoxyethylene bl cks bf the average formula: HO(CzH4O)' C Ha bonded to silicon EXAMPLE 4 Eight mixtures were prepared from the following ingredients:

- Identified in Example 1.

This example illustrates the secondary expansion provided by a fluorocarbon boiling at about 48 C. The viscosity of each resulting mixture was well below 10,000 cps. after holding it at 24.5 to 25.5 C. for 2600 seconds.

Each mixture A through H was mechanically beaten as set forth in Example 1 for minutes to form a froth having a density as listed in Table III. Each froth was stable both structurally and chemically for at least 50 minutes and cured to a tack-free, ifiexible foam having the density listed in Table III within less than 10 minutes at 125 C. or less.

TABLE III Froth Foam density density l Identified in Table II by number listed. M03510[MG2SiO11lB11O (CaHeO)itcaHosiMeohslMeg 8 50 wt. percent [(CH3)3$100.5]0.5[S10z]1,0 1D. Polyol I.

Poly0l III, as used herein, designates a. mixture of diols and triols' prepared by adding ethylene oxide and propylene oxide to a mixture of 4 mols glycerol and 1 mol dipropylene glycol, in a ratio providing an average of 14 Wt. percent oxyethylene units and 86 wt. percent oxypropylene units based on the total oxyalkylene units. The hydroxyl number is 45.8 to 48.8 and the average molecular weight is about 3700. f m n as used herein designates a polyisocyanate of the ormu a BITCO NCO] NCO 'CaHaCHr- CoHa' n-CH2CBH4 is sold by The Carwin Company under the designation PAPI and has the following properties:

Isocyanate equivalent (dibutylamine) 133.5 Viscosity (centipoises at 25 C.) 250 Hydrolyzable chloride (percent) 0.35 Specific gravity (20/20 C.) 1.2 Flash point (Cleveland Open Cup), h 425 N00 content by weight, percent minimum -2-.. 31 Insoluble solids content Nil Each mixture A through E was mechanically beaten as set forth in Example 1 for 10 minutes to form a froth having a density as listed in Table IV. Each froth was stable both structurally and chemically for at least 60 minutes and each provided the drainage rate as listed in Table IV. Each froth was cured to a tack-free, flexible foam within less than 10 minutes at 125 C. or less.

TABLE IV Drainage, m1. drained per ml. froth at- Surfactant Froth Mixture 0. density 30 min. 60 min.

1 Identified in Table II by number listed.

EXAMPLE 6 A mixture was prepared from the following ingredients:

Wt. pts. Polyol I 100.0 'IDI 26.0 Nickel acetylacetonate 0.5 I:( 3)3 o.5]0 5[ 2]1.o*

*50 wt. percent solution in xylene.

The viscosity of the mixture was about 450 cps. after holding at 24.5 to 25.5 C. for 2600 seconds.

The mixture was frothed in the manner described in Example 1 by beating for 10 minutes at a speed setting of 2. The resulting froth had a density of about 10 pounds per cubic foot and was coated onto a substrate to a onequarter inch thickness. The coated substrate was cured for 5 minutes at C. to provide a tack-free, mediumcelled, uniform foam having a density of about 8 pounds/ cu. ft.

EXAMPLE 7 This example illustrates a range of foam densities and rates of froth drainage obtainable by the practice of this invention.

Eleven mixtures were prepared from the following ingredients:

. Wt. pts. Polyol 1V 95.0 Polyol V 5.0 Prepolymer 3 20.6 Surfactant (as listed in Table V) 10.0 Nickel acetylacetonate 0.5

1 Polyol IV is a glycerol-started, ethylene oxide-propylene oxide adduet triol having at average molecular weight of about 3525 and an average hydroxyl number of about 48 and having the average formula Polyol V is a blend having an average hydrgxyl number of about 785 and contains about 13.5 parts of ethylene glycol and about 86.5 parts of a glycerol-started ethylene oxide adduct triol having an average molecular weight of about 269 and the average formula:

3 Prepolymcr is prepared by reacting S4 weight parts of TDI as identified in Example 1 and 16 weight parts of Polyol II to the extent that 32.5 wt. percent of the prepolymer are free NCO groups. The viscosity of each resulting mixture was well below 10,000 cps. after holding it at 24.5 to 25.5 C. for 2600 seconds.

Each mixture A through I was mechanically beaten as set forth in Example 1 for 10 minutes to form a froth having a density as listed in Table V. Each froth was stable both structurally and chemically for at least 50 minutes and cured to a tack-free, semi-flexible foam having the density listed in Table V within less than 10 minutes at 125 C. or less.

TABLE V Drainage m1, drained per 100 ml. froth at-- Surfactant Froth Foam N 0. density density 30 min. 60 min See Table II for identification of Surfactant Nos. 1 through 9. See Table III for identification of Surfactant No. 11.

The partially crosslinked block copolymers useful as surfactants in this invention (e.g., surfactant No. 9 in Table II above) can be produced by the addition of a mixture of suitable polyoxyalkylene polymers to a hydrogensiloxane. A suitable mixture of polyoxyalkylene polymers is composed of a linear polyoxyalkylene polymer endblocked with a hydroxy group and a alkenyloxy group and a linear polyoxyalkylene endblocked with two alkenyloxy groups. The addition reaction is conducted in the presence of a chloroplatinic acid catalyst and a basic compound (e.g., sodium carbonate or sodium bicarbonate). A suitable process is disclosed in US. patent application Serial No. 790,830 filed Jan. 13, 1969, now abandoned.

We claim:

1. A process for preparing a cured polyurethane foam consisting essentially of:

(1) forming a substantially non-aqueous mixture comprising (a) an organic polyisocyanate,

(b) a polyhydroxyl-containing compound substantially reactive with said polyisocyanate only at a temperature of at least 70 C. to form a polyurethane,

16 (c) an organosilicon surfactant for structurally stabilizing the froth produced according to step (2) below, during the period that the liquid phase of said froth is chemically stable and until said froth is cured by heating to a temperature of at least 70 C. to produce a cured'foam, and (d) a catalyst having substantial catalytic activity in the curing of said mixture only at temperatures of at least 70 C.; p H (2) substantially uniformly dispersing inert gas throughout the mixture by mechanical beating of said mixture to form a heat curable froth which is substantially structurally and chemically stable, but workable at ambient conditions, wherein (i) said froth is free of auxiliary blowing agents,

(ii) components (a), (b), (c) and (d) above, present in the liquid phase of said froth are such that an unfrothed admixture containing only (a), (b), (c) and (d) in the same proportions (a), (b), (c), and (d) are present in the liquid phase of said froth is chemically stable to the extent that the admixture retains a viscosity of not greater than 10,000 cps. for about 2600 seconds at 25 C.i0.5 C.;

(iii) said froth has a density of not greater than 45% of the density of the unfrothed liquid phase; and

(iv) a A inch section of said froth is curable to a tack free condition in not more than about 30 minutes at a temperature of 125 C.; and

(3) heating said froth at a temperature at least 70 C.

to form a cured polyurethane foam, any further expansion of said froth during heat curing being substantially only thermal expansion of said inert gas employed.

2. A process as defined in claim 1, wherein said inert gas is air.

3. A process as defined in claim 1, wherein said catalyst is nickel acetylacetonate.

4. A process as defined in claim 1, wherein said inert gas is introduced into the mixture under pressure and the mechanical beating is conducted at a pressure not greater than p.s.i.g.

5. A process as defined in claim 1, wherein said inert gas is drawn into the mixture from the overlying atmosphere and the mechanical beating is conducted at about atmospheric pressure.

6. A process as defined in claim 1, wherein said mixture also contains a filler.

7. A process as defined in claim 1, wherein said organosilicon surfactant is an organosilicon surfactant consisting essentially of Si0 units and (CH SiO units in a mol ratio of about 0.8 :1 to 2.0: 1, respectively.

8. A process as defined in claim 1, wherein said organosilicon surfactant is a partially crosslinked siloxanepolyoxyalkylene block copolymer composition wherein the blocks are linked by silicon to carbon linkages or silicon to oxygen to carbon linkages, the siloxane blocks are comprised of hydrocarbon-siloxane groups and have 'an average of at least two valences of silicon per block combined in said linkages, at least a portion of the polyoxyalkylene blocks are comprised of oxyalkylene groups, having at least two valences of carbon or carbon-bonded oxygen per block combined in said linkages, any remaining polyoxyalkylene blocks are comprised of oxyalkylene groups having only one valence of carbon or carbonbonded oxygen per block combined in saidlinkages.

9. A process as defined in claim 1, wherein said organosilicon surfacant is a siloxane-polyoxyalkylene block copolymer.

10. A process as defined in claim 1, wherein said froth has a density of not greater than 35% of the density of the unfrothed liquid phase.

11. A process as defined in claim 1, wherein said polyisocyanate is pre-reacted with a phenolic compound resulting in a blocked polyisocyanate having a splitting temperature of at least 70 C.

12. A process as defined in claim 1, wherein the polyisocyanate is an aromatic polyisocyanate or mixtures thereof; and wherein said polyhydroxyl compound is selected from the group consisting of a polyether polyol, a polymer/polyol of an ethylenically unsaturated monomer and a polyether polyol, a cyclic ester polymer, and mixtures thereof.

13. A process as defined in claim 1, wherein said inert gas is air, nitrogen or carbon dioxide; wherein said catalyst is nickel acetylacetonate; wherein the inert gas is present in the mixture as a result of having been introduced under pressure and the mechanical beating is conducted at a pressure not greater than 100 p.s.i.g.; wherein a filler is also present in the mixture; and wherein said froth has a density of not greater than 35% of the density of the unfrothed liquid phase.

14. A process as defined in claim 13, wherein said inert gas is air.

15. A process as defined in claim 14, wherein the polyisocyanate is an aromatic polyisocyauate or mixtures thereof; and wherein said polyhydroxyl compound is selected from the group consisting of a polyether polyol, a polymer/polyol of an ethylenically unsaturated monomer and a polyether polyol, a cyclic ester polymer, and mixtures thereof. I

16. A process as defined in claim 15, wherein said aromtic polyisocyanate is selected from the group consisting of tolylene diisocyanate, bis(4-isocyanatophenyl)methane, polyphenylmethylene polyisocyanate, a prepolymer of tolylene diisocyanate and any one of the polyhydroxyl compounds as herein defined above, and mixtures thereof.

17. A process as defined in claim 16, wherein said organosilicon surfactant is a member selected from the group consisting of an organosilicon surfactant consisting essentially of Si units and (CH SiO units in a mol ratio of about 0.8:1 to 2.021, respectively, and a siloxauepolyoxyalkylene block copolymer.

18. A process as defined in claim 17, wherein said polyisocyanate consists essentially of tolylene diisocyanate and said polyhydroxyl compound consists essentially of a poly- UNITED STATES PATENTS 3,523,103 8/1970 Zemlin 2602.5 3,474,075 10/1969 Zemlin 260-77.5 3,432,474 3/1969 Lombardi 260-2.5 3,291,660 12/1966 Oberth 260-77.5 3,194,773 7/ 1965 Hostettler 260-2.5 3,706,681 12/1972 Bachura 2602.5 BD 3,108,976 10/1963 Knox 2602.5 AF

FOREIGN PATENTS 822,546 10/1959 Great Britain 260-2.5 AF 803,771 10/ 1958 Great Britain 2602.5 AF 707,380 4/1965 Canada 2602.5 AF 707,381 4/1965 Canada 2602.5 AF

OTHER REFERENCES Foam Bulletin Frothing Processes For Urethane Foams, by R. E. Knox; Du Pont; EL-1l96; June 22, 1960.

Benning: Plastic Foams: The Physics and Chemistry of Product Performance and Process Technology; Wiley, Interscience; N.Y., 1969; p. 139.

DONALD E. CZAJ A, Primary Examiner C. W. IVY, Assistant Examiner U.S. Cl. X.R.

156-72; 161-67, 159, 190; 260-2.5 AB, 2.5 AF, 2.5 AH, 2.5 AM, 2.5 AN, 2.5 AT, 2.5 AP; 264-45, 47, 

